Epoxy acetals



United States Patent 3,255,214 EPOXY ACETALS Benjamin Phillips and PaulS. Starcher, Charleston,

W. Va., assignors to Union Carbide Corporation, a corporation of NewYork No Drawing. Original application June 17, 1959, Ser. No. 820,871,now Patent No. 3,018,294, dated Jan. 23, 1962. Divided and thisapplication Aug. 14, 1961, Ser. No. 131,422

5 Claims. (Cl. 260-348) This invention relates in general to a new classof organic compounds and more particularly to novel epoxy acetals andmethods for their preparation.

Thi application is a division of application Serial No. 820,871, filedJune 17, 1959, now US. Patent No. 3,018,294, issued January 23, 1962.Application Serial No. 820,871 is a continuation-in-part of applicationSerial No. 645,010, filed March 11, 1957, now abandoned.

The novel epoxy acetals of the present invention can be convenientlyrepresented by the following general formula:

wherein R is a member selected from the class consisting of monovalentaliphatic, alicyclic and aromatic groups and wherein at least one Rcontains the epoxy group,

and at least one R contains an additional group which is a memberselected from the class consisting of epoxy and olefinic groups.Preferred compounds represented by the aforesaid formula are thosewherein R contains from 1 to 22 carbon atoms and more preferably from 3to 18 carbon atoms in any one chain or group originating at thealdehydic carbon atoms. When the Rs which are attached to the ethericoxygen atoms contain epoxy groups they must contain at least 3 carbonatoms. Ptarticularly preferred epoxy acetals are those compounds whereinR is alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl,bicycloalkenyl, bicycloalkenylalkyl, and

wherein at least one double bond in the molecule has been converted tothe epoxy group.

It should be noted that the novel acetal compounds of this invention are(ii-functional or poly-functional in that each compound contains atleast two reactive groups, one of which must be an epoxy group. Forexample, the novel epoxy acetals encompassed by the first embodiment ofthe present invention as hereinafter described, contain one epoxy groupand at least one unsaturated double bond. The other embodiments containtwo or more epoxy groups and additionally can also contain olefinicunsaturation as well.

By the term aliphatic, as hereinbefore employed, is meant a groupcomposed of carbon, hydrogen, and in some instances oxygen and includessuch groups as alkyl, alkenyl, alkoxy, epoxyalkyl, epoxyalkenyl,epoxyalkoxy, aralkyl, and the like. By the term alicyclic as employedthroughout the specification and appended claims is meant a groupcomposed of carbon, hydrogen, and in some instances, oxygen and includessuch groups as cycloalkyl, bicycloalkyl, cycloalkenyl, bicycloalkenyl,epoxycycloalkyl, epoxy bicycloalkyl, and the like.

By the term epoxyalkyl as employed throughout the specification andclaims is meant an alkyl group to one pair of vicinal carbon atoms ofwhich oxirane oxygen is attached.

Due to the presence of the epoxy group,

\C C/ o the novel compounds of this invention are useful in thepreparation of epoxy resins. Particularly noteworthy, are the diandtri-epoxy acetals which form excellent compositions when hardened withpolyamines, polyacids, anhydrides, and the like. Additionally, the epoxyacetals which contain one or more double bonds are useful as monomersfor copolymerization with vinyl compounds to give coatings and filmswhich may be cross-linked through the epoxy group itself. These novelcompounds are likewise of particular interest'as precursors in thepreparation of unsaturated glycols which are useful in the synthesis ofvulcanizable polyurethanes. Thus, the unsaturated monoepoxy acetals suchas the aldehyde alkenyl epoxyalkyl acetals are attractively useful inthe manufacture of high purity alkanetriols such as glycerol, 1,9,10-octadecanetriol, 2-ethyl-1,2,3-hexanet1iol, and the like. Thealkanetriols thus formed are themselves useful solvents for a variety oforganic chemicals, as hardeners for epoxy resins and as intermediates inthe manufacture of a large variety of chemicals. The novel epoxy acetalsof this invention are also valuable as stabilizers forchlorinecontaining resins. For example, the novel compounds of thisinvention containing two epoxy groups have been found useful asplasticizers with vinyl halide resins. By incorporating into the resinfrom about 5 to about 50 percent by weight of these novel diepoxides, aplasticized product is obtained which possesses useful resihent andflexible characteristics. The vinyl halide resins which can besatisfactorily plasticized by the compounds. of this invention can beany vinyl halide polymer such as polyvinyl chloride, vinylchloride-vinyl acetate copolymers, vinyl chloIide-acrylonitrilecopolymers, vinyl chloridevinylidene chloride copolymers, vinylchloride-vinylidene chloride-acrylonitrile copolymers, and the like. Thecom pounds of this invention may be used alone or in conjunction withconventional plasticizers.

A particularly interesting novel class of compounds included within thescope of the present invention embraces epoxy acetal compounds whichcontain a reactive double bond in the molecule as well as the epoxygroup. These compounds are especially useful and differ from compoundslacking unsaturation in that they can be converted to polymers througheither the oxirane ring or the polymerizable double bond and thereaftercrosslinked through whichever of these two was not used in the initialpolymerization. Many of the resulting polymeric materials are useful aslubricants and as hydraulic fluids where high temperatures areencountered. Thus,

the epoxy acetals of this invention which contain a polymerizable bondare particularly useful since they can be incorporated into polymersthrough the polymerizable linkage and the epoxy group subsequently usedfor crosslinking the resin.

It is accordingly an object of the present invention to provide neworganic compounds which are suitable for use in the plastic and resinfield. Another object is to provide new compositions of mattercomprising the epoxy acetals. A further object of the present inventionis to provide novel compounds comprising the monoepoXy acetals. Anotherobject is to provide novel acetals containing more than one epoxy group.A still further object of the present invention is to provide novelcompounds having bifunctional properties in that they contain both epoxygroups and active double bonds within the same molecule. Another objectof the present invention is to pro- .vide novel compounds'containingepoxy groups which are part of a cycloaliphatic ring. A further objectof the present invention is to provide novel compounds containing epoxygroups which are part of a bicycloaliphatic ring. A still further objectis to provide processes for the preparation of the novel compositions ofmatter of this invention. These and other objects will readily becomeapparent to those skilled in the art in the light of the teachingsherein set forth.

In its broad aspect, this invention is directed to novel epoxy acetalsof the aforementioned formula and methods for their preparation andencompasses novel difunctional epoxy acetals containing one or moreepoxy groups. Thus, within the scope of the present invention are thosecompounds wherein R of the above formula can be alkyl, aryl, cycloalkyl,aralkyl, alkaryl, alkoxy, alkenyl, cycloalkenyl, cycloalkenylalkyl,bicycloheptenyl, dihydrodicyclopentadienyl, and wherein at least one Rcontains an epoxy group. In the novel acetals containing only one epoxygroup at least one double bond must be present in the molecule. Forexample, typical compounds illustrative of the novel epoxy acetals ofthe present invention include Acetaldehyde allyl glycidyl acetal,

Acetaldehyde oleyl 9,10-epoxystearyl acetal,

Butyraldehyde allyl glycidyl acetal,

Acetaldehyde Z-methyl-Z-propenyl 2-methyl-2,3-

epoxypropyl acetal,

Benzaldehyde allyl glycidyl acetal,

3,4-epoxy-6-methylcyclohexanecarboxaldehyde diallyl acetal,

3-oxatricyclo [3 .2. 1.0 octane-6-carboxaldehyde diethyl acetal,

Benzaldehyde diglycidyl acetal,

Butyraldehyde di(2,3-epoxybutyl) acetal,

5,5-di(6-rnethyl-3,4-epoxycyclohexylmethoxy)-l-pentene,

bis(3,4-epoxy-6-methylcyclohexylmethyl) 3,4-epoxy-6-methylcyclohexanecarboxaldehyde acetal,

bis(9,l-epoxystearyl)3,4-epoxy-6-methylcyclohexanecarboxaldehyde acetal,

6-methyl-3 -oxatricyclo[3.2.1.0 ]octane-7ecarboxaldehydedi(1-methy1-3,4-epoxycyclohexylmethyl) acetal,

1,1,3-tri(2,3-epoxypropoxy)propane,

1,2-epoxy- ,5 -di 6-methyl-3,4-epoxycyclohexylrnethoxy pentane,

and the like.

One embodiment of the present invention encompasses those novel epoxyacetal compounds represented by the general formula:

wherein R is as previously indicated and an epoxy group is present inonly one of the R groups; the remaining two Rs having at least oneolefinic bond between them and being aliphatic, alicyclic, or aromaticgroups or combinations thereof. The epoxy group can be present on anyone of the R groups as part of a straight chain, branched chain, or partof a ring. Preferred compounds within the breadth of this embodimentwould include among others the aldehyde alkenyl epoxyalkyl acetals,epoxyaldehyde dialkenyl acetals, epoxyaldehyde alkyl alkenyl acetals,epoxyaldehyde alkenyl aryl acetals, alkyl aldehyde alkenyl epoxyalkylacetals, aryl aldehyde alkenyl epoxyalkyl acetals, and the like.Additionally, alkyloxy, alkaryl, aralkyl, cycloalkyl, cycloalkenyl,polycycloalkyl and polycycloalkenyl may be substituted for the alkyl, oraryl groups of the above compounds. It is thus evident that the instantembodiment of the present invention embraces those compounds where anepoxy group is present in any one of the three R groups and at least oneR contains an olefinic double bond. The remaining R groups can bealiphatic, alicyclic or aromatic groups or combinations thereof. Whilethe monoepoxy acetals are the preferred compounds of this embodiment,acetals containing more than one epoxy group in the same R are intendedto be included in the scope of this invention.

The aldehyde alkenyl epoxyalkyl acetals, referred to above as apreferred class within the above embodiment of the present invention,are also referred to as the unsaturated monoepoxy acetals, and can berepresented by the class formula:

wherein R is a monovalent group and is a member selected from the classof aliphatic, alicyclic, and aromatic groups; -(C H represents analkenyl group; (C H O) is an epoxyalkyl group wherein O representsoxirane oxygen; and n is an integer from 1 to 22 and preferably 3 to 18;with the limitation that n have a value greater than 2 for theepoxy-containing group. Preferred aldehyde alkenyl epoxyalkyl acetalsare those represented by the foregoing formula in which R contains from1 to 18 carbon atoms, particularly 1 to 12 carbon atoms, since acetalshaving more than 18 carbon atoms in the R group, while being useful, arenot economically feasible. Preferred aldehyde alkenyl epoxyalkyl acetalsare those which can be represented by the foregoing formula in which Ris alkyl or aryl. Thus, alkyl aldehyde alkenyl epoxyalkyl acetals andaryl aldehyde alkenyl epoxyalkyl acetals are preferred. Particularlypreferred unsaturated monoepoxy acetals within this embodiment are thosein which R is alkyl.

The unsaturated monoepoxy acetals can be prepared by the epoxidation ofthe olefinic double bonds of corresponding aldehyde dialkenyl acetalswith suitable epoxidizing agents. The aldehyde dialkenyl acetal startingmaterials can be represented by the formula:

O(CnH2n-l) wherein R and n are previously defined. Typical epoxidizingagents are the peracids, e.g., peracetic acid, perpropionic acid,perbenzoic acid, and the like, or the aldehyde monoperacylates, e.g.,acetaldehyde monoperacetate and propionaldehyde monoperpropionate. Ofthese epoxidizing agents, the 2 to 3 carbon aliphatic peracids,particularly peracetic acid, and the 2 to 3 carbon aliphatic aldehydemono-(2 to 3 carbon aliphatic)-peracylates, particularly acetaldehydemonoperacetate, are preferred mainly from the aspect of beingeconomically available and capable of producing commercially acceptableyields.

The epoxidation employing a peracid can be represented by the followingequation:

represents a peracid and Xt|3OH represents the residue from the peracidafter epoxidation. Epoxidations employing aldehyde monoperacylates canbe represented similarly. Many epoxidizing agents in crystalline form orhighly concentrated solutions are highly explosive when exposed tophysical shocks, sometimes of the very slightest magnitude. Possibleexplosion hazards are avoided by preventing the formulation ofcrystalline forms or highly concentrated solutions of epoxidizing agent.This can be safely accomplished by employing in the epoxidationsolutions containing below about 60 weight percent of epoxidizing agent.Ethyl acetate and'acetone are two of the many solvents available forperacetic acid or acetaldehyde monoperacetate. It is particularlyimportant that the epoxidation be carried out in the absence of heavymetal ions or strong acids and water so as to avoid the hydrolysis ofthe easily hydrolyzableacetal starting materials and products.

The epoxidation is advantageously carried out at temperatures in therange of 0 to 100 C. At temperatures below this range epoxidation takesplace at a very slow rate and above this range side reactionslproduceundesired materials and reduce the yield. Molar ratios of epoxidizing.agent to aldehyde dialkenyl acetal starting material can be varied overa wide range, for example, from 0.1 to 1.6, with molar ratios of 1.0 orbelow being preferred, however. Molar ratios above 1.6 may be employed,although the formation of other materials brought about by such higherratios usually necessitates extensive separation methods. Molar ratiosbelow 0.1 may also be employed, but the low yield of product makes theuse of such ratios impractical. The epoxidation time required to produceour aldehyde alkenyl epoxyalkyl acetals will depend upon the epoxidationtemperature, the molar ratios employed and the yield desired. Anysuitable method for isolating the product, such as, fractionation,crystallization and the like can be employed.

A typical epoxidation which uses acetaldehyde diallyl acetals asstarting material to produce the acetaldehyde allyl glycidyl acetalillustrates the method used to produce the several aldehyde alkenylepoxyalkyl acetals of our invention. In this typical epoxidation, a 22.6weight percent solution of peracetic acid in acetone was addedcontinuously over a period of 3 hours to acetaldehyde diallyl acetal.The molar ratio of peracetic acid to the acetal was about 0.36 and thetotal weights of reactants were 304 grams of peracetic acid and 1577grams of the acetal. The temperature of the reaction mixture during theaddition of peracetic acid was maintained at about 50 C. and thereaction mixture was continually stirred during the entire addition.After adding all of the peracetic acid the reaction mixture was stirredfor 4 additional hours while maintaining the temperature at about 50 C.At the end of this period, titration to determine peracetic acid contentby conventional methods indicated that about 93.1 percent of theacidoriginally charged had been consumed. The reaction mixture was thencooled to room temperature.

The cooled reaction mixture was fed into ethylbenzene refluxing atreduced pressure and stripped of low-boiling materials, e.g., acetone,unreacted peracetic acid, and acetic acid (as an azeotrope withethylbenzene), leaving a residue. The residue was then fractionated toprovide 399 grams of acetaldehyde allyl glycidyl acetal. This amount ofproduct represented a 68 percent yield based on theoretical.Acetaldehyde allyl glycidyl acetal, thus formed, had a boiling point of91 C. to 95 C. at 20 millimeters of mercury reduced pressure and asodium light index of refraction of 1.4322 at 30 C.

Similar epoxidations can be performed on other aldehyde dialkenylacetals with, however, the replacement of acetaldehyde diallyl acetal,-respectively, by

' dation described above.

6 Stearaldehyde diallyl acetal, Acetaldehyde di(2-ethyl-2-hexenyl)acetal, and Isobutyraldehyde diallyl acetal,

to produce, respectively,

Benzaldehyde allyl glycidyl acetal,

Acetaldehyde crotyl 2,3-epoxybutyl acetal,

Acetaldehyde oleyl 9,10-epoxystearyl acetal,

Butyraldehyde allyl glycidyl acetal,

Butyraldehyde crotyl 2,3-epoxybutyl acetal,

Propionaldehyde oleyl 9,10-epoxystearyl acetal,

Acetaldehyde Z-methyl-Z-propenyl 2-methyl-2,3-epoxy propyl acetal,

Phenylacetaldehyde allyl glycidyl acetal,

Phenylacetaldehyde oleyl 9,10-epoxysteary1 acetal,

Stearaldehyde allyl glycidyl acetal,

Acetaldehyde 2-ethyl-2-hexenyl 2-ethyl-2,3-epoxyhexyl acetal, and

Isobutyraldehyde allyl glycidyl acetal.

Molar ratios of peracetic acid to the respective aldehyde dialkenylacetals, reaction temperatures and approximate reaction times of all ofthese epoxidations are essentially the same as the molar ratio, reactiontemperature and reaction time of the acetaldehyde dialkenyl acetalepoxi- Separations of the products are conducted by procedures which aresimilar to the separation procedures described above for isolatingacetaldehyde allyl glycidyl acetal or by any other suitable separationmethods and the percent yields are of the same approximate magnitude.

Aldehyde dialkenyl acetals which are starting materials in theproduction of the aldehyde alkenyl epoxyalkyl acetals of this embodimentof the present invention can be prepared by methods known in the art. Atypical preparation of an aldehyde dialkenyl acetal is by the reactionof the corresponding alkenyl alcohol and the corresponding aldehyde inthe presence of calcium chloride, as described by Hurd and Pollack,Journal of American Chemical Society, 60, 1906 (1938). Several othermethods of preparing the starting materials are known.

A second embodiment of the present invention encompasses those novelcompounds represented by the general formula:

wherein R is as previously indicated and epoxy groups are present in twoof the R groups and the remaining R is a saturated or unsaturatedaliphatic, alicyclic or aromatic group. As indicated in the previousembodiment, the

epoxy groups can be present as part of a straight chain,

branched chain, or part of a ring. Preferred compounds within thebreadth of this embodiment would include, among others, the

Alkyl aldehyde di-epoxyalkyl acetals,

Aryl aldehyde di-epoxyalkyl acetals,

Alkyl aldehyde di-cpoxycycloalkyl acetals,

Alkyl aldehyde epoxycycloalkyl epoxyalkyl acetals, Aryl aldehydeepoxycycloalkyl epoxyalkyl acetals, Ep-oxyalkyl aldehyde epoxyalkylalkyl acetals, Epoxyalkyl aldehyde epoxyalkyl aryl acetals,Epoxycycloalkyl aldehyde epoxyalkyl alkyl acetals, Epoxycycloalkylaldehyde epoxyalkyl aryl acetals, Alkenyl aldehyde di-(epoxyalkyl)acetals,

Alkenyl aldehyde di-(epoxycycloalkyl) acetals, Alkenyl aldehydeep'oxycycloalkyl epoxyalkyl acetals,

and the like. It should be noted that the instant invention is intendedto embrace those compounds wherein the epoxy groups may be present inany two R groups and the remaining R group may be saturated orunsaturated. Thus, for example, compounds within this embodiment ineludethe class of aldehyde di-(epoxyalkyl) acetals which can be prepared fromthe corresponding aldehyde dialkenyl acetal by the process of theinstant invention.

Benzaldehyde diallyl acetal,

Acetaldehyde dicrotyl acetal,

Acetaldehyde dioleyl acetal,

Butyraldehyde diallyl acetal,

Butyraldehyde dicrotyl acetal, Propionaldehyde dioleyl acetal,

Acetaldehyde di(2-methyl-2-propenyl) acetal, Phenylacetaldehyde diallylacetal, Phenylacetaldehycle dioleyl acetal, Stearaldehyde diallylacetal,

Acetaldehyde di(2-ethyl-2-hexenyl) acetal, and Isobutyraldehyde diallylacetal can be epoxidized to produce respectively,

Benzaldehyde diglycidyl acetal,

Acetaldehyde di(2,3'epoxybutyl) acetal, Acetaldehydedi(9,10-epoxystearyl) acetal, Butyraldehyde diglycidyl acetal,

Butyraldehyde di(2,3-epoxybutyl) acetal, Propionaldehydedi(9,10-epoxystearyl) acetal, Ace-taldehyde di(2-methyl-2,3-epoxypropyl)acetal, Phenylacetaldehyde diglycidyl acetal, Phenylacetaldehydedi(9,10epoxystearyl) acetal, Stearaldehyde diglycidyl acetal,

Acetaldehyde di(2-ethyl-2,3-epoxyhexyl) acetal, and Isobutyraldehydediglycidyl acetal.

While the diepoxy acetals are the preferred compounds within the scopeof this embodiment, acetals containing more than one epoxy group in eachof the two Rs are intended to be included in the breadth of thisinvention.

An additional preferred class of novel epoxy acetal compounds Within thescope of the aforesaid second embodiment of the present invention wouldinclude those compounds represented by the following formula:

O-(CnH2n-1O) R-GH (CnH2n1O) wherein R, 12 and -(C H O) are as previouslyindicated.

The aldehyde dialkenyl acetals which are starting materials in theproduction of the aldehyde diepoxyalkyl acetals of this embodiment ofthe present invention can be prepared by methods known to the art. Forexample, butyraldehyde diallyl acetal is a known compound and wasstudied by Davison and Bater, J. Chem. Soc., 2607-11 (1953). Thereaction of alkenyl alcohols and aldehydes in the presence of calciumchloride to give aldehyde dialkenyl acet-als is described by Hurd andPollack, J.A.C.S., 60, 1906 (1938). Several other methods for preparingthe starting compounds are known.

A third embodiment of the present invention encompasses those novelcompounds represented by the general formula:

wherein R is as previously indicated and an epoxy group is present ineach of the R groups. As indicated in the previous embodiments, theepoxy groups can be present as part of a straight chain, branched chain,or part of a rmg.

A preferred class within this embodiment include the noveltri-(epoxyalkyl) acetals having the formula:

I n zn1 0 Ha-0P0 H ()(C nH2n-10) wherein -(C H O) represents anepoxyalkyl group wherein 0 represents oxirane oxygen and n is an integerfrom 3 to 18.

Preferred compounds Within the scope of this embodiment would include,among others,

1,1,3-tri-(2,3-epoxypropoxy) propane,3,4,-epoxy-6-methylcyclohexanecarbox aldehyde bis(9,10-

epoxystearyl) acetal,1,2-epoxy-S,5-di-(6-methyl-3,4-epoxycyclohexylmethoxy) pentane,3,4-epoxy-6-me-thylcyclohexanecarboxaldehyde bis(3,4-

epoxy-6-methylcyclohexylmethyl) acetal, 6-methyl-3-oxatricyclo[3.2.1.0octane-7-carboxaldehyde di-(l-methyl-3,4-epoxycyclohexylmethyl) acetal,

and the like. Additionally, compounds containing more than one epoxygroup in each of the three R groups are included within the scope of theinstant invention.

In accordance with the process of this invention, the novel epoxy acetalcompounds of the three aforementioned embodiments canbe produced in highyields by the epoxiclation of the olefinic linkage contained in theunsaturated acetal. starting material. In the epoxy acetals preparedfrom compounds containing only one double bond, 'the epoxidation iseffected quite easily. In the acetals prepared from unsaturatedcompounds having more than one site of unsaturation, it has beenobserved that epoxidation can occur selectively. Thus, by appropriatecombinations of different oletinic groups an essentially completeselectivity can be achieved in the preparation of many epoxy acetals.Compounds which contain double bonds of approximately the samereactivity toward epoxidation can usually not be selectively epoxidizedunless the epoxidizing agent is reacted with a large excess of diolefin.

In a preferred embodiment of the process of the present invention, theepoxidation of the unsaturated starting materials is carried. out attemperatures in the range of from 25 C. to 150 C. At the lowertemperatures, the rate of epoxidation is slow, while at the highertemperatures, the rate is faster necessitating precautions to preventfurther reaction of the epoxide groups. In order to avoid undesired sidereactions and to provide a suitable reaction rate, temperatures in therange of from 10 C. to C. are preferable. In the practice of theinvention, the unsaturated starting material is conveniently charged toa reaction vessel and the appropriate quantity of peracetic acid isadded. The mole ratio is not necessarily critical and can be varied overa wide range depending on whether the mono-, di-, or higher epoxycompound is desired. The reaction is allowed to proceed for a timesufficient to consume approximately the theoretical quantity ofperacetic acid needed to effect epoxidation. The amount of peraceticacid consumed can be determined by periodic tests for peracetic acid.Usually from about one to about ten hours is suflicient for the reactionto be completed at the preferred temperature. It is preferred, althoughnot absolutely necessary, to separate the by-product acetic acid fromthe epoxide rapidly, since the acetic acid will react with the epoxideto form undesired products, decreasing the overall yield. Finally, thereaction mixture is subjected to conventional recovery procedures toisolate the epoxyester. Extraction with a suitable solvent, continuousdistillation, or distillation under reduced pressures all are applicableto the recovery of the epoxidized compound.

The following examples illustrate the practice of this invention:

Example I.-Preparati0n of 1,1 ,3-tri-(2,3-ep0xypr0p0xy)- butane To 452grams of 1,1,3-trialloxybutane (from the reaction of crotonaldehyde withallyl alcohol) which was heated With stirring to 50 C.55 C., there wasadded 1955 grams of a 27.2 percent solution of peracetic acid in ethylacetate dropwise over a period of five hours.

9 After an additional three hours the reaction was 91 percent completeas indicated by analysis for unreacted peracetic acid. The cooledreaction mixture was passed through a steam-heated stripper once at apressure of 50 millimeters of mercury and again at 5 millimeterspressure to remove the volatiles from the product. The stripped productwas then flash-distilled to give an almost colorless liquid, which uponanalysis gave 80 percent as 1,1,3-tri-(2,3-epoxypropoxy) butane by thepyridine hydrochloride method, in 63 percent yield based on peraceticacid. A sample of this product was redistilled through a short Vigreauxcolumn to give colorless material, 87.5 percent as1,1,3-tri-(2,3-epoxypropoxy) butane, boiling point 154/0.6 millimeter, n30/D 1.4593.

Example lI.Preparatin of 1,1,3-tri- (2,3-epoxypr0p0xy) propane To 424grams of 1,1,3-triallyloxypropane, prepared from allyl alcohol andacrolein by the method outlined in US. 'Patent 2,561,254, which wasmaintained with stirring at 55 C.60 (3., there was added 1980 grams of a26.9 percent solution of peracetic acid in ethyl acetate dropwise over aperiod of five hours. After an additional two hours at 60 C., thereaction was 96.7 percent complete as indicated by titration forunreacted peracetic acid. The reaction mixture was passed through asteamheated stripper once at a pressure of 50 millimeters of mercury andagain at a pressure of 7 millimeters to remove the volatiles from theyproduct. The stripped product was then flash distilled to give 285 gramsof 1,1,3- tri-(-2,3-epoxypropoxy)propane which contained 10.55 percentoxirane oxygen as determined by the pyridine hydrochloride method.

Example III.-Preparati0n of 6-methyl-3-cycl0hexenecarboxaldehyde diallylacetal A mixture of 671 grams mols) of6-me-thyl-3-cycl-ohexenylcarboxaldehyde, 870 grams mols) of allylalcohol, 500 grams of benzene, and 7.5 grams of paratoluenesulfonic acidwas charged to the kettle of a still equipped with a fractionationcolumn. The reaction mixture was heated under reflux at atmosphericpressure for a period of 22 hours, during which time 111 cubiccentimeters of lower layer (constant boiling mixture of allyl alcohol,benzene, and Water) separated in the still head.

The catalyst was neutralized with sodium ethoxide, and

the reaction mixture was distilled under pressure. There was obtained 653 grams (59 percent yield) of 6-methyl- 3-cyclohexenecarboxaldehydediallyl acetal having the following properties: boiling point, 113 C. at5 millimeters pressure; refractive index 1.4698 (n 30/D), density at 270., 0.9375.

Analysis.Calculated for C H O C, 75.67; H, 9.97. Found: C, 75.47; H,9.87.

The infrared spectrum was consistent with the assigned structure.

Example IV.Preparati0n of 3,4-epoxy-6-metlzylcyclohexanecarboxaldehydediallyl acetal To 389 grams (1.726 mols) of6-methyl-3-cyclohexenecarboxaldehyde diallyl acetal was added dropwise,over a period of 95 minutes, 510 grams of a 28.3 percent solution ofperacetic acid (1.9 mols)) in ethyl acetate at a temperature of 30 C.After an additional 1.5 hour reaction period 96 percent of thetheoretical amount of peracetic acid (for the monoxide) had beenconsumed. The reaction mixture was then fed dropwise to the kettle of astill containing 500 grams of ethylbenzene which was heated under refluxat such a pressure as to maintain a kettle temperature of C. Ethylacetate, acetic acid, and excess peracetic acid were removedcontinuously. The product was purified by fractional distillation to0btain 273 grams of 3,4-epoxy-6-methylcyclohexanecarboxaldehyde diallylacetal, a colorless liquid having the following properties: boilingpoint, 126 C. at 2 millimeters; n 30/D=l.4730; purity by the pyridinehydrochloride method of analysis, 99.1 percent.

Analysis.Calculated for C I-1 0 C, 70.56; H, 9.29. Found: C, 70.55; H,9.14.

Example V.Pr'eparation of 6-methyl-3-cycl0hexenecarboxaldehydebis(6-methyl-3-cycl0hexenylmethyl) acetal A mixture of 373 grams (3mols) of 6-methyl-3-cyclohexenecarboxaldehyde, 1010 grams (8 mols) of6-methyl 3-cyclo-hexenylmethanol, 1000 cubic centimeters of toluene, and6.9 grams of p-toluenesulfonic acid was charged to a still equipped witha fractionating column and a decanter-type still head. The mixture washeated under reflux and the water removed continuously as it was formed.After 8 hours, 53 cubic centimeters of water had been removed. Thecatalyst was neutralized by adding 3.3 grams of sodium acetate and 25cubic centimeters of percent ethanol in which 1 gram of sodium had beendissolved. The reaction mixture was flash-distilled through a one-platecolumn and then fractionated in a second distillation. There wasobtained 858 grams of 6-methyl-3-cyclohexenecarboxaldehyde bis(6-methyl-3-cyclohexenylmethyl) acetal, a colorless liquid having thefollowing properties: boiling point 210 C. at 3 millimeters; n30/D=1.5010; D 25.5=0.9819.

Analysis.Calculated for C H O C, 80.36; H, 10.78. Found: C, 80.45; H,10.85.

The infrared spectrum was consistent with the proposed structure.

Example VI..Preparation of 3,4-epoxy-6-methylcyclohexanecarboxyaldehydebis(3,4 epoxy 6 methyleyclohexylmethyl) acetal To a solution of 200grams (0.559 mol) of 6-methyl-3- cyclohexenecarboxaldehydebis(6-methyl-3-cyclohexenylmethyl) acetal in grams of ethylbenzene wasadded 555 grams of a 28.8 percent solution of peracetic acid (2.1 mols)in ethyl acetate over a period of 30 minutes at a temperature of 40 C.After an additional reaction period of 1.67 hours at 40 C.,' thetheoretical amount of peracetic acid had been consumed. An additional500 grams of ethylbenzene was used to help remove the acetic acid andother volatiles from the product by codistillation. After stripping to akettle temperature of 80 C. at 8 millimeters pressure, there wasobtained 291 grams of a residue product which had the followingproperties: viscous pale yellow liquid, analysis bypyridine-hydrochloride method for epoxide=87.4 percent calculated as3,4-epoxy-6-methylcyclohexanecarboxaldehydebis(3,4-epoxy-6-methylcyclohexylmethyl) acetal, iodine number=2.3,acidity calculated as acetic acid=0.2 percent.

Example VII.Preparati0n of 6-methyl-3-oxatricyclo- [3.2.1.0 ]0ctane 7carboxaldehyde di(] methyl- 3',4-ep0xycycl0hexylmethyl) acetal A. 3methylbicyclo[2.2.1] 5 heptene 2 carboxaldehydedi-(1-methyl-3-cycl0hexenylmethyl) acetal. A weight of 136 grams (1 mol)of refined 3-methylbicyclo-[2.2.1]-5-heptene-2-carboxaldehyde was mixedWith 315 grams (2.5 moles) of 1-rnethyl-3-cyclohexenylmethanol andrefluxed in the presence of 500 milliliters of ethylene dichloride and 4grams of p-toluenesulfonic acid. When 18 grams of water had been removedby distillation, the reaction mixture was neutralized and filtered overanhydrous sodium sulfate. Subsequent distillation gave 193 grams (52percent of the theoretical yield) of 3-methj yl-bicyclo[2.2.1]-5-heptene-2-carboxaldehyde di( l-meth- 1 1yl-3-cyc10hexenylmethyl) acetalat a boiling point of 96100 C. at 0.1millimeter (n 30/D=1.4861-1.5003). Analysis by iodine valuedeterminations gave a value of 206 compared to a theoretical of 205.6.

B. 6 methyl 3 oxatricyclo[3.2.1.0 ]ctane 7 carboxaldehyde di (1 methyl3,4 epoxycyclolzexylmethyl acetal.-A weight of 83 grams (0.224 mole) of3-meth" ylbicyclo[2.2.1]--heptene-2-carboxaldehyde di( 1-methyl-S-cyclohexenylmethyl) acetal was allowed to react with 206 grams (0.751mole) of a 27.7 percent of peracetic acid'in ethyl acetate at 25 C. to30 C. for a 45-minute period. The consumption of peracid by the olefinwas complete at that time. Conventional azeotropic removal(ethylbenzene) of the volatile components of the reaction mixtureprovided a non-distillable residue product which analyzed 47.5 percentas the expected triepoxide, 6-rnethyl-3-oxatricyclo[3.2.1.00ctane-7-carboxaldehyde di(1- methyl-3,4-epoxycyclohexylmethyl) acetal.

Example VIII.-Preparati0n 0 5 ,5-di(6-metlzyl-3,4-ep0xycyclohexylmethoxy)-1-pentene A. 5,5di(6-methyl-3-cycl0hexenylmethoxy) 1 pentene.A mixture of 96 grams (1.38mole) of 4-pentenal, 428 grams of 6-methyl-3-cyclohexenylmethanol, 500milliliters of ethylene dichloride and 3 grams of p-toluenesulfonic acidwas refluxed at atmospheric pressure until no more water was observed atthe still head attached to the reaction vessel (21 period ofapproximately three hours). After neutralization of the catalyst,distillation of the reac tion mixture gave 158 grams (36 percent of thetheoretical yield) of 5 ,5-di 6-methyl-3 -cyclohexenylmethoxy l penteneat a boiling point of 142 C.-145 C. at 0.6 millimeter (n30/D=1.48281.4848; I Value=243; Theory 1 Value=239).

B. 5,5 di(6 methyl 3,4 epoxycyclolzexylmetlzoxy)- 1-pentene.A weight of74.5 grams (0.234 mole) of 5,5-di(6-methy1-3-cyclohexenylmethoxy)1-peutenewas allowed to react with 165grams (0.6 mole) of a 27.7 percent solution of peracetic acid in ethylacetate over a two hour and minute period at 40 C. After that period,analysis showed that two moles of peracid per mole of olefin used hasbeen consumed. The volatile components of the reaction mixture wererapidly removed by vacuum evaporation to provide 82 grams of a residueproduct (quantitative yield) which analyzed 96.6 percent pure as5,5-di(6-methyl 3,4 epoxycyclohexylmethoxy)-1-pentene (n 30/D=1.4862).

Infrared absorption studies showed that no unsaturation remained in thecyclic six-membered rings while the terminal unsaturation remained.

. 12 Example IX .Preparation of 1,2-ep0xy-5,5-di-(6-methyl-3,4-ep0xycycl0hexylmethoay pentane A weight of 70 grams (0.22 mole) of5,5-di(6-methyl- 3-cyclohexenylmethoxy)-l-pentene was allowed to reactat C. with 219 grams (0.80 mole) of a. 27.7 percent solution ofperacetic acid in ethyl acetate for a period of three and one-halfhours. At that time, analysis showed 98 percent of the available peracidequivalent to the olefin employed had been consumed. The coproductacetic acid was then removed as an azeotrope with ethylbenzene. Removalof the excess ethylbenzene gave a residue product which by analysiscontained 74.8 percent of the expected triepoxide. Subsequentreduced-pressure distillation gave 49 grams (60.8 percent of thetheoretical yield) of 1,2- epoxy-5,5 di(6 methyl 3,4epoxycyclohexylmethoxy) pentane, boiling point202 C.205 C. at 0.1millimeter; n 30/D=1.4888-1.4891; purity by pyridine hydrochloridemethod=98.7 percent.

Although the invention has been illustrated by the preceding examples,the invention is not to be construed as limited to the materialsemployed in the above examples, but rather, the invention encompassesthe generic invention as hereinbefore disclosed. Various modificationsand embodiments of this invention can be made without departing from thespirit and scope thereof.

We claim:

1. .Acetaldehyde allyl glycidyl acetal.

2. Acetaldehyde oleyl 9,10-epoxystearyl aceta 3. Butyraldehyde allylglycidyl acetal.

4. .Acetaldehyde 2-metbyl-2-propenyl 2-methyl-2,3-epoxypropyl acetal.

5. Benzaldehyde allyl glycidyl acetal.

References Cited by the Examiner UNITED STATES PATENTS 2,719,089 9/1955Lovell 260-348 2,917,521 12/1959 Phillips et a1 260348.5 3,043,8137/l962 Kilsheimer et a1 260348 3,081,343 3/1963 Merten 260348 OTHERREFERENCES Fourneau et al.: Bull. Soc. Chim. 12, 845-64 (1945),

page 863 relied on.

WALTER A. MODANCE, Primary Examiner.

IRVING MARCUS, Examiner.

JAY P. FRIEDENSON, NORMA S. MILESTONE,

Assistant Examiners.

1. ACETALDEHYDE ALLYL GLYCIDYL ACETAL.